REACTIONS  OF  CARBON  SUBOXlDPi: 
WITH  HYDROXYLAMINES 


BY 


FRED  W.  SACKETT 


THESIS 

FOR  THE 

DEGREE  OF  BACHELOR  OF  SCIENCE 


CHEMISTRY 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1922 


ti" 


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it: 


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Sa  / 


UNIVERSITY  OF  ILLINOIS 


THIS  IS  TO  CERTIFY  THx\T  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 
FPJ^B  UAPD  SACKUTT 


ENTITLED REACTIONS  OF  CARBON  STOOXIDE  Y.MTTT  Tr>DRn>P,HC-YIINFS 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REOUIREMENTS  FOR  THE 


DEGREE  OF M^IHELOR 


Instructor  in  Charge 


Approved 


ACTINO  HEAD  OF  DEPARTMENT  OF  __QHSMIS[CEy_L 


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AcloioviTleilsement 


This  opportunity  is  taken  to  express  appreciation  for  the 
suggestions  and  criticisns  of  Dr.  Charles  D.  Hurd  which  were  of 
material  assistance  to  the  experiment. 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/reactionsofcarboOOsack 


CONTENTS 


Page 


I.  Introduction  1 

II.  Experiuental  4 

III.  Sumnary  9 

IV.  Bililiograpliy  10 


I 


REACTIONS  OF  CARBON  SUBOXIDE  FITII  HYDROXYL  AJ.IINES . ! 

1 

I . INTRODUCTION . | 

i 

Among  the  classes  of  organic  compounds  which  have  been  | 

! 

I 

brought  to  light  more  or  less  recently  are  the  ketenes,  compounds  | 

! 

containing  the  atomic  grouping,  :C:C:0  . They  were  discovered  in  ; 

(1)  I 

1005  by  Staudinger  wBo  prepared  diphenyl  ketene,  (CqII|5)2:C:C:0  , I 

by  distilling  (CgH^ )2C1C-C0C1  Virith  zinc,  in  ether  solution.  The 

(2) 

nex^  year  Diels  and  Wolf  prepared  carbon  suboxide,  0;C:C:C:0  . | 

Subsequently  more  than  a dozen  other  ketenes  have  been  formed  with  I 
a consecpient  investigation  of  many  of  their  characteristic  reac- 
tions. 

As  may  be  expected  from  the  unsaturated  nature  of  the  charac- 
teristic grouping,  ketenes  enter  into  addition  reactions  readily. 
Witli  ketenes  water  produces  carboxylic  acids,  alcohols  give  esters, 
and  acids  yield  anhydrides . With  basic  compounds  the  following 
reactions  are  characteristic: 

(1)  Ammonia  produces  amides, 

HgC : C : 0 t-  NII3  CH3CONII2 

(2)  Aniline  gives  anilides, 

(CH3)2C:C:0  tH2N(GgH5)  — ^ H (CH3  )2C-C0NH  (C6H5  ) 

An  interesting  parallel  may  be  found  in  the  case  of  the  iso- 
cyanates which  possess  a characteristic  grouping  similar  to  that 
of  the  ketenes,  namely  RN:C;0  . 


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-2- 

(1)  With  annionia, 

CoIl5N:C:0  NHp,  --  CpH5NIir0XIl2 

(2)  T.^ith  aniline, 

CgII^N:C:0  HoNCgHs  CgllgNIICONHCgHg 

Ilydroxylamine  has  also  been  allov/ed  to  react  with  isocyanates 
Thus  the  reaction: 


(3)  i 


+ HNHOH  CgHr^N-gO 
6 5 6 oJ-j 


Nil  on 

Until  last  year,  a siniilar  reaction  ^vith  the  ketenes  had  never 

been  studied.  On  the  Tjasis  of  the  addition  of  hydro xj-lariines  to 

the  isocj'anates,  however,  it  could  have  been  predicted  that  ketenes 

(4) 

would  respond  similarly.  Jones  and  Hurd  found  this  to  be  the 
case  with  diphenyl  ketene.  The  addition  product  was  diphenj’-l-acet- 
< hydroxamic  acid: 


(CgH5)C:C:0  ITNIIOH  (CfiH,;)C“CO 


H NIIOH 

In  order  to  develop  this"  work’ further  carbon  suboxide  was 
chosen  as  the  keteiie.  Its  structure,  0;C:C:C:0,  makes  it  partic- 
ularly interesting,  possessing  as  it  does, essentially  two  charac- 
teristic ketene  groups  in  the  molecule.  Diels  and  Wolf  first 

formed  it  by  treating  diethyl  malonate  with  |Jhosphorus  pentoxide. 

(5) 

Later  Diels  and  Meyerheim  prepared  it  by  similar  treatment  of 

malonic  acid  and  a variety’  of  malonic  acid  derivatives.  Stauding- 

(6) 

er  and  St.  Bereza  are  responsible  for  the  development  of  the 
preparation  of  the  suboxide  in  a manner  characteristic  of  the 


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preparation  of  ketenes  in  general . They  prepared  it  in  ether  sol- 
ution, dehalogenating  dihron-malonyl chloride  by  distillation  of  an 
ether  solution  of  the  acid  halide  with  zinc  turnings.  This  method 
of  preparation  has  been  followed  in  this  work.  At  ordinary  temp-  \ 

eratiires  cai*bon  suboxide  is  a gas,  b.p.  7°;  m.p.  -107®,  and  there-  f 

! 

fore  the  preparation  of  the  pjii'e  compound  involves  several  diffi-  | 

! 

culties  which  are  avoided  in  the  method  used.  The  compound  in  eth-! 
er  solution  sufficed  for  the  reactions  carried  out.  | 

Diels  and  ^ITolf  found  that  its  general  behavior  follov/s  that 
which  is  characteristic  of  all  ketenes.  It  reacts  with  water  to 
form  malonic  acid: 

0 : C : C : C : 0 -f-  2n0H  COgll -CH^COgH 

It  is  considered  as  the  anliydride  of  the  acid  inasmuch  as  the  true 
anhydride,  C-CH2-C,  has  never  been  isolated.  It  adds  ammonia  to 
form  the  amide,  and  aniline  to  give  malon3"l  anilide.  With  hydrox- 
j’^l^amine,  as  brought  out  by  Jones  and  ITurd,  the  reaction  should 
lead  to  the  formation  of  the  hydroxamic  acid  of  malonie  acid: 

0:C:C:C:0-r2NHo0H  ) 

NIIOIl"'  NIIOH 

Were  the  ketene  to  be  reacted  with  an  hj^droxamic  acid,  inter- 
est arises  as  to  the  manner  in  which  the  reaction  would  proceed. 
There  are  several  possibilities  open,  and  if  we  consider  both  of 
the  ketene  groups  as  taking  part  in  the  reaction  the  two  most  like- 
ly reactions  are: 

(1)  V/itli  the  alpha  hydrogen  of  the  hydroxamic  acid,  thus: 

Q.  0 H 0 0 0 

0:C;C:C:0f  HONHC-n  —i  n-C-S-O-C-CHo-d-O-NII-C-R 


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(2)  With  the  beta  hydrogen,  thus: 

no  0 0 

0:C:C:C:0  i-HONHCOR  ->  R-C-N-C-CHg-C-N-C-R 

on  on 

Of  these  two  possibilities  the  first  seems  more  probable  in  the 

light  of  the  manner  in  which  hydroxamic  acids  are  known  to  react 

with  acyl  groups.  If  one  acyl  group  is  added,  there  are  no  cases 

on  record  where  the  beta  hydrogen  is  acetylated  before  the  alpha 

in  an  hj-droxamic  acid.  Kith  acetic  anhydride  we  have: 

OH  0 0 0 

R-C-.Til0Ht(CH3-C0)20  R-C-N-0-C-Cn3 1 CIIg-C-OH 


II.  EXPERBIENT AL . 

Malonic  acid  was  used  as  the  starting  point  in  the  prepara- 
tion of  the  ketene,  bromination  of  the  acid  to  form  dibrom-malonj'^l 

(7) 

chloride  being  the  first  step  as  described  by  Conrad  and  Reinbach. 
One  mole  of  the  acid  reacts  with  two  moles  of  bromine,  thus: 

COgH-CHo-COgH  -h  2Br^  COoH-CErp-COgH  -f  2HEr 

72  g.  of  moist  malonic  acid  was  dissolved  in  60  c.c.  of  di- 
lute HCl  in  a round  bottom  flask  immersed  in  an  ice  bath  and  182  g. 
of  bromine  introduced  slowly  with  constant  agitation  of  the  flask. 
The  amount  of  halogen  added  was  the  amount  computed  to  be  necessary 
to  brominate  60  g.  of  pure  acid(the  amount  of  acid  estimated  to  be 
contained  in  the  original  72  g.)  After  all  the  bromine  was  run  in, 
the  dibrom  compound  crystallized  out  and  was  filtered  with  suction. 


(i 


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It  was  then  dried  in  a vacuum  desiccator.  130  g.  of  dry,  white 
crystals  resulted. 

The  dihrom-malonylchloride  was  prepared  according  to  the 

(8) 

method  of  Staudinger  and  St.Eereza  in  which  130  g.  of  the  dibrom 
compound  dissolved  in  400  c.c.  of  absolute  ether  is  added  to  230  g. 
of  phosphorus  pentachloride  at  such  a rate  as  the  reaction  permits. 
The  reaction  is: 


COgH-CBr^-CO^Ht  2PC1^  —V  COCl-CBr^-COCl -f  2P0Clg -f  2HC1 


The  130  g.  of  dibrom-malonic  acid  was  dissolved  in  a proportionate 
amount  of  absolute  ether  and  run  into  a flask  containing  the  PCl^ 
with  a condenser  attached  and  the  mixture  refluxed  for  two  hours. 

The  ether  was  then  distilled  and  the  portion  remaining  was  fractionjf 
ated  at  a pressure  of  15-20  mm.,  the  fraction  coming  over  from 
70-80  degrees  being  saved  and  redistilled.  40  g.  of  the  acid 
chloride  was  obtained  as  contrasted  to  the  yield  of  144  g.  report- 
ed by  the  originators  of  the  method. 

This  preparation  was  used  for  the  generation  of  the  suboxide 

(9) 


according  to  the  method  developed  by  Staudinger  and  St.  Bereza 
who  report  that  30  g.  of  the  acid  halide  dissolved  in  300  c.c.  of 
absolute  etlier  was  added  to  20  g.  of  zinc  turnings  in  a liter 
flask  at  such  a rate  that  the  solution  boiled  briskly.  The  ether 
solution  containing  the  ketene  was  collected  by  means  of  an  ice 
cooled  condenser  and  receiver.  10  g.  of  the  halide  was  dissolved 
in  a proportionate  amount  of  absolute  ether  and  a portion  of  the  s 
solution  dropped  upon  zinc  turnings  in  a flask  by  means  of  a drop- 
ping funnel . The  reaction  was  rather  slow  in  starting  but  soon 


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-6- 

developed  with  sufficient  vigor  and  heat  as  t6  cause  some  of  the 
into 

ethei*  to  distil  A^he  receiver  whicli  was  immersed  in  an  ice  hath. 

The  remainder  of  the  acid  chloride  solution  was  added  as  the  vigor 
of  the  reaction  subsided  and  it  was  necessary  to  apply  heat  to  the 
flask  in  order  to  cause  the  reaction  to  go  beyond  a certain  stage, 
most  of  the  ether  thereby  being  distilled  into  the  receiver. 

The  ether  distillate (which  contained  theoretically  somewhat 
more  than  two  grams  of  the  suboxide)  was  divided  into  two  gqual 
portions,  one  portion  being  shaken  with  2 c.c.  of  water  and  the 
other  with  2 g.  of  aniline.  The  ether  was  then  removed  and  it  was 
found  that  a small  amount  of  malonic  acid  was  formed  with  the  water 
reaction  and  a trace  of  the  anilide  in  the  case  of  the  solution  in- 
to which  aniline  was  introduced.  Such  yields  were  disappointing 
as  it  was  felt  that  more  of  the  ketene  had  been  formed  than  the  re- 
sults would  seem  to  indicate.  This  conclusion  was  reached  from  the 

ketenoj 

seeming  A’-igor  of  the  reaction  wliich  produced  theA*the  sharp  odor 
at  times  very  perceptible  during  the  operations,  and  the  vapor 
pressure  above  the  ether  solution  of  suboxide  vdien  the  latter  was 
agitated.  This  last  seemed  to  indicate  that  considerable  of  the 
gas  had  never  dissolved  in  the  solvent  or  had  escaped  from  solution 
whentthe  ether  was  agitated.  It  was  concluded  that  perhaps  better 
results  could  be  obtained  by  exposing  the  distillate  to  the  reac- 
tion Liixtiire  directly  upon  evolution  of  the  suboxide.  This  was  ac- 
complished by  submerging  the  end  of  the  condenser  into  t’le  solution 
containing  the  substance  with  which  it  was  desired  to  have  the  ke- 
tene react.  About  14  g.  of  the  nalonyl  chloride  was  dropped  upon 
the  zinc  turnings  in  the  second  run  with  the  above  modification  in 


W'%'  ' ;l'vy  -'V‘^  v:  .^:  ,■  ■ ;■  . :,v  Vv^ . v/vv; My  r 

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-7- 


procecliire , appro:^iiaatel3f  two-thirds  of  the  distillate  hein^^  run 
through  a solution  of  water  in  ether  and  the  remainder  tlirough  an 
ether-aniline  solution.  O.IO  g,  of  inalonic  acid  and  0.25  g.  of  the 
anilide  resulted,  proving  that  the  carhon  suhoxide  liad  been  gener- 
ated in  some  quantity.  By  computing  the  amount  of  ketene  necessarjj'' 

I 

for  the  formation  of  the  alaove  quantities  of  compounds  it  was 
found  that  11.5  o/o  of  the  theoretical  yield  of  ketene  had  reacted. 
Staiidinger  and  St.  Bereza  report  80  o/o. 

The  suhoxide  was  then  allov/ed  to  react  with  hj'droxylajnine. 

The  latter  was  prepared  hy  treating  its  hydrochloride (impure)  in 
methanol  solution  with  the  calculated  amount  of  a solution  of  sod- 
ium meth3’’late.  Approximately  2 c.c.  of  free  hj’droxj’-l^amine  was 
obtained  by  fractional  vacuum  distillation.  This  was  introduced 
into  a flask  containing  35  c.c.  of  ether (absolute) . 15  g.  of  the 

acid  chloride  was  dropped  upon  the  zinc  turnings  and  the  distillate 
conducted  directly  into  the  ether-Iij'droxj^lamine  mixture.  A vdiite 
precipitate  v/as  soon  noticeable  in  the  ether  as  the  distillate 
came  over.  At  the  completion  of  t!ie  reaction  a considerable  por- 
tion of  the  hj’’drox3^1  amine  remained  in  the  bottom  of  the  flask,  im- 
miscible v/ith  the  ether.  The  flask  and  contents  were  allowed  to 

disappeared 

stand  for  several  hours  with  occasional  shaking.  The  precipitate  ^ 
and  it  was  concluded  that  the  small  quantity  of  immiscible  liquid 
had  extracted  the  precipitate  from  the  ether  layer.  The  ether  was 
distilled  and  t!ie  remaining  solution  was  placed  in  a vacuum  desic- 
cator. About  0.25  g.  of  residue  remained  which  gave  a pronounced 
red  color  with  ferric  chloride.  It  was  somewhat  soluble  in  water, 
slightly  soluble  in  alcohol,  and  insoluble  in  ether.  Aqueous  so- 


-8- 

I 

liitions  and  alcoholic-ethcr  solutions  of  the  residue  tlirev;  dov/ii  a 

precipitate  when  treated  with  dilute  ammonium  hydroxide.  This  was 

expected  since  Hantzscli  described  the  insoluble  anuiionium  acid  salt, 

(10) 

HNOn-CO-CIIo-CO-NITONTI^.  The  precipitate,  with  no  purification,  melt' 
ed  at  107-110°,  and  decomposed  at  a slightly  higher  temperature. 

In  order  to  attempt  a reaction  with  carbon  suboxide  and  an 
hydroxamic  acid,  1 g.  of  benzhydroxamic  acid  was  dissolved  in  fjp  c. 
e.  of  ethyl  acetate  and  the  suboxide,  generated  from  10  g.  of  the 
acid  chloride,  passed  into  the  solution.  As  the  solution  still 
gave  a color  reaction  with  ferric  chloride,  a one-sixth  portion  of 
the  reaction  mixture  was  taken,  and  the  ketene  passed  into  it  until 
the  ferric  chloride  test  showed  that  no  benzhydroxamic  acid  re- 
mained. About  8 g.  of  the  acid  chloride  v;as  required  for  this. 

To  obtain  the  reaction  product  the  ether  and  ethyl  acetate 
were  removed  by  evaporation  and  the  residue  dissolved  in  wara  alco- 
hol, and  filtered.  The  filtrate  was  diluted  with  water,  causing  a 
tardy  separation  of  white  crystals.  More  of  these  crystals  were 

''5'  That  described  by  Hantzscli  melted  at  141®. 

During  this  experiment  It  developed  that  it  was  probaTble  that 

some  of  the  ketene  was  being  lost  through  cork  connections  of  the 

apparatus,  so  rubber  was  substituted  througliout . This  forced  all 

benz 

of  the  ketene  through  the  solution  in  the  flask  containing  the/^^hy- 
droxamic  acid.  Apparently  this  jirecaution  was  justified  by  the  re- 


sults 


V \ V'  "Vl 

w i:  V K t*’^‘tt?  ••  wtA»t,*^  tiii^fc-ytatf  ^ '.r*'Jt;fi^-*^  uatii^iu  t ^ J. 

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14 


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<r'K  ,'jii^t,i'-i'.:»Y  i)©*^ii;)j^tn  v'*Ti:noi<iP  x'.-'tJ- ^0  . 

p .f  _-’  'A-  r*»^  ' ■■  Y -■■-  V . •'■■■  , " 


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(!»  :H;*.  Iiv;»'id'*,!,.xi;rt  * SinH’iJtfividim  KiiW  aaVlTn^r 

K.  u . ^rtfia:  # ••  ;■  .ifi  ..  ...■  m > ..  'V'i 

ll^  H •Mf.t  nJt  no:tJfU*nf  t<d^  ■wfvt  .j^.i 


^Ji>/ift^•.^t<J  til  fto.Uwl‘*«*  ■3trfvt :j^ 

- 5"»*  »i:fli  ^i;j  p«4i8<|«(A  . f).f:n*j  OtiJWXo'Tjti 

' ,*-  ' -"•  t ' ' L-^  ' '-Ci’.-  ■ •.  ",PJ 


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1^  ■■■  ’ ^ r ^.,\V  f ..  . ■*  ' A* 


tiv  ...rC  kd(ili/je. 


,.‘i 


-9- 

recovered  from  the  reaction  mixture  which  still,  contained  free 
benzhydroxaniic  acid  as  shovm  by  the  color  reaction  v.^lth  ferric 

chloride.  Here  also  the  solvent  was  evaporated  and  the  residue 
dissolved  in  alcohol,  the  crystals  being  precipitated  by  dilution 
with  water.  The  benzhydroxamic  acid,  which  is  soluble  in  both  al- 
cohol and  water,  remained  in  the  filtrate.  In  all  about  0.1  to  0,2 
g.  of  the  recrystallized  compound  was  obtained. 

From  the  vierwpoint  that  carbon  suboxide  is  an  acylating  agent 

this  compound  should  be  the  malonyl  ester  of  benzhydroxamic  acid, 

0 0 

Clio  (C-0-NH-C-Cr-II- • It  melted  sharr)ly  between  151^  and  152^.  It 
is  insoluble  in  water,  and  in  ligroin.  It  dissolves  readily  in  al- 
cohol. A solution  of  it  does  not  react  with  ferric  chloride. 


Ill,  SUIUIAnY. 

1.  A ketene,  carbon  suboxide,  was  prepared  by  treating  di- 
brom-malonyl  chloride  with  zinc  turnings. 

2.  The  suboxide  was  reacted  with  hydroxj'l amine  yielding  a 
product  which  responded  to  several  tests  characteristic  of  malonyl 
hydroxamic  acid,  the  compound  it  was  expected  would  result. 

3.  The  ketene  was  reacted  with  benzhydroxamic  acid  and  a c 
corapound  obtained  which  was  thought  to  be  the  malonj’l  ester  of  benz- 
hydroxamic acid. 


-10 


BiULIOGRAPIIY. 


(1) 

Ber. , 

38, 

1735 

(1005). 

(2) 

Ber. , 

39, 

689 

(1900). 

(2) 

Kjellinj  Ber., 

2G,  2384 

(1893) . 

(4) 

Jour . 

.^ner 

•.  Chem.  Soc., 

43,  2422  (1921). 

(5) 

Ber . , 

40, 

355 

(1907). 

(6) 

Ber . , 

41, 

4461 

(1908) . 

(7) 

Ber . , 

35, 

1817 

(1902). 

(3) 

Ber . , 

41, 

4464 

(1908). 

(9) 

Ibid. 

(10)  Ber., 

27, 

799 

(1894) . 

